EP2964566A1 - Précurseurs de nanoparticules en chalcogénure de cuivre-indium-gallium pour cellules solaires en couches minces - Google Patents

Précurseurs de nanoparticules en chalcogénure de cuivre-indium-gallium pour cellules solaires en couches minces

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Publication number
EP2964566A1
EP2964566A1 EP14728626.4A EP14728626A EP2964566A1 EP 2964566 A1 EP2964566 A1 EP 2964566A1 EP 14728626 A EP14728626 A EP 14728626A EP 2964566 A1 EP2964566 A1 EP 2964566A1
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Prior art keywords
nanoparticles
temperature
thiol
thiols
mmol
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German (de)
English (en)
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EP2964566B1 (fr
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James Harris
Christopher Newman
Ombretta Masala
Laura Wylde
Nigel Pickett
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Nanoco Technologies Ltd
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Nanoco Technologies Ltd
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    • B82—NANOTECHNOLOGY
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • This invention relates to photovoltaic materials. More particularly, it relates to the fabrication of Culn x Gai -x S2 (0 ⁇ x ⁇ 1 ) nanoparticles.
  • photovoltaic cells must generate electricity at a cost that is competitive with fossil fuels.
  • the photovoltaic cells must be made using low cost materials and by inexpensive device fabrication processes. Photovoltaic cells must be capable of moderate to high conversion efficiency of sunlight to electricity. And the materials synthesis and device fabrication must be commercially scalable.
  • the photovoltaic market is currently dominated by silicon wafer-based solar cells (a.k.a. first-generation solar cells).
  • the active layer in these solar cells is made of single-crystal silicon wafers having a thickness typical ly ranging from a few microns to hundreds of microns, a thickness that is relatively large. A thick active layer is required because silicon is relatively poor at absorbing light.
  • These single-crystal wafers are relatively expensive to produce because the process involves fabricating and slicing high-purity, single-crystal silicon ingots. The yield of that process is often low.
  • Copper indium diselenide (CulnSe 2 ) is one of the most promising candidates for thin film photovoltaic applications.
  • solar cells based on CulnSe 2 can be made by selenizing films of CulnS 2 .
  • films of CulnS 2 are heated in a selenium-rich atmosphere, causing selenium to replace sulphur in some or all locations within the film, because when Se replaces S the substitution creates volume expansion, which reduces void space within the film and reproducibly forms a high quality, dense CulnSe 2 absorber layer.
  • a CulnS 2 nanoparticle film may be converted to a predominantly selenide material by annealing the film in a selenium- rich atmosphere.
  • CulnS 2 nanoparticles are a promising as precursors for producing the CulnSe 2 active layer.
  • An advantage of using CulnS 2 nanoparticles instead of simply using CulnSe 2 nanoparticles is that the sulphur precursors are usually less expensive and more readily available than their selenium counterparts.
  • the theoretical optimum bandgap for absorber materials is about 1 .3-1 .4 eV.
  • the bandgap can be manipulated so that, following selenisation, the Culn x Gai -x Se 2 absorber layer has an optimal bandgap for solar absorption.
  • the nanoparticle ink or paste may be deposited using low-cost printing techniques such as spin coating, slit coating or doctor blading.
  • Printable solar-cells may replace the standard, conventional vacuum-deposited methods of manufacturing solar cells because the printing processes, especially when implemented in a roll-to-roll processing framework, enables a much larger throughput.
  • Nanoparticles of the ternary CulnS 2 system have been prepared with various synthetic methods including the hot-injection method, solvothermal techniques, and thermal decomposition of suitable precursors.
  • Colloidal nanoparticle synthesis typically employs high temperatures (above 250°C), to form small ( ⁇ 20 nm), organic-capped nanoparticles.
  • colloidal nanoparticles display lower melting points than the bulk material.
  • Such nanoparticles often have a narrow melting temperature range because the nanoparticles are highly monodisperse (i.e., the diameters of the nanoparticles are within a narrow size distribution).
  • the method described in the ⁇ 04 Application does not demonstrate tunability to synthesise Culn x Gai -x S2 nanoparticles and does not demonstrate that tailoring of the initial metal ratio and choice of reagents can be used to obtain the desired stoichiometry. Further, to employ the reaction temperatures described in the ⁇ 04 Application, a high- temperature boiling thiol is required.
  • the hot-injection route usually consists of injecting a solution of sulphur in an appropriate solvent, such as trioctylphosphine (TOP) or oleylamine (OLA), into a solution of copper and indium salts at high temperature.
  • TOP trioctylphosphine
  • OVA oleylamine
  • Zn-doped CulnS 2 nanoparticles have been prepared via this method at temperatures between 160- [0013] 280°C [H. Nakamura et al., Chem. Mater., 2006, 18, 3330].
  • a drawback of hot-injection techniques is that it is difficult to control the reaction temperature on a large scale, so reactions are generally restricted to milligram scales and typically require large reaction volumes.
  • Single-source precursor (SSP) methods for nanoparticle synthesis employ a single compound that contains all of the constituent elements to be incorporated into the nanoparticle. Under thermolysis, the SSP decomposes leading to nanoparticle formation.
  • CulnS2 nanoparticles were prepared by using precursors of the type (PR 3 ) 2 Cu(SR) 2 ln(SR) 2 , where R is an alkyl group.
  • Dutta and Sharma used the xanthate precursors ln(S 2 COEt) 3 and Cu(S 2 COEt) in ethylene glycol at 196°C to obtain tetragonal CulnS 2 with an average size of 3-4 nm, with occasional aggregation [D . Dutta and G. Sharma, Mater. Lett., 2006, 60, 2395].
  • the CulnS 2 nanoparticles prepared by these SSPs displayed very poor solubility and a tendency to form micron-sized aggregates because non-coordinating solvents were employed. SSP processes are complicated than other methods because they require an extra step to synthesise the precursors.
  • the method outlined by Wang et al. can be used to synthesise Culn x Gai -x S 2 nanoparticles across the entire 0 ⁇ x ⁇ 1 range, the nanoparticles are capped with high boiling ligands: OLA (348-350°C), TOPO (201 -202°C at 2 mm Hg, which equates to 397-399°C at atmospheric pressure), 1 -DDT (266-283°C) and/or tert-DDT (227-248°C).
  • OLA 348-350°C
  • TOPO 201 -202°C at 2 mm Hg, which equates to 397-399°C at atmospheric pressure
  • 1 -DDT 266-283°C
  • tert-DDT 227-248°C
  • Chang et al. describe the synthesis of the quinary nanoparticles in the range 0 ⁇ x,y ⁇ 1 , which enables tuning of the bandgap from 0.98-2.40 eV [S-H. Chang et al., Energy Environ. Sci., 201 1 , 4, 4929].
  • CuCI, InCb and/or GaCb, Se and/or S were mixed with OLA, then purged with Ar at 130°C for 1 hour under vigorous stirring. The solution was heated to 265°C then held for 90 minutes, after which the reaction was quenched in a cold water bath.
  • the reaction was held at 225°C for 30 minutes, then cooled and isolated by centhfugation with toluene/ethanol.
  • the resulting nanoparticles have a very low organic content ( ⁇ 10%), making them insoluble in organic and polar solvents and difficult to process as a printable ink.
  • a U.S. Pat. No. 7,892,519 describes an SSP method for producing Cu(ln,Ga)S2 nanoparticles capped with a thiolate ligand.
  • the disclosure only exemplifies methods to synthesise CulnS 2 .
  • the synthetic methods described in the prior art generally produce large nanoparticles that have a tendency to aggregate and are insoluble in most solvents. This is an important issue because it is desirable to produce small and soluble nanoparticles that may be further processed to formulate an ink to make inorganic films by conventional and low-cost techniques like printing or spraying.
  • Capping ligands such as hydrocarbons, can be associated with the surface of the nanoparticles to aid in the processibility.
  • the synthetic procedures described above are carried out at a high temperature, which limits the choices of capping ligands to those ligands having a relatively high vaporization/decomposition temperature.
  • the present method yields small CulnS 2 and Culn x Gai -x S 2 nanoparticles (with sizes down to about 2.5 nm in diameter and generally in the range 2.5 nm to about 10 nm) with narrow size distributions.
  • the nanoparticles may be capped with a volatile alkyl thiol and are soluble in a range of solvents.
  • the nanoparticles may be dispersed in a solvent, such as toluene, to formulate an ink that may be deposited to form CulnS 2 or Culn x Gai- XS 2 films using conventional low-cost printing techniques like spraying, doctor-blade coating, bar coating, ink-jet printing and the like.
  • Nanoparticles made using the disclosed process generally have a lower melting point compared to bulk material and pack more closely, which facilitates coalescence of the particles during melting, resulting in improved film quality. This allows lower processing temperatures, opening the possibility of using flexible substrates (for example, paper and plastic) as components in PV cells. Because melting point can change with particle size, nanoparticles having a narrow size distribution will melt approximately at the same temperature, producing a high quality film.
  • a significant advantage provided by the use of a low-boiling alkyl thiol is that it can be easily and cheaply removed from the nanoparticles by mild heating. This is important because carbon impurities from ligand residues remaining in the film after the baking process may cause deterioration in the performance of the solar cell.
  • Another advantage is that the alkyl thiol acts both as a sulfur source and as a ligand, which simplifies the synthesis.
  • Figure 1 shows an absorption spectrum of CulnS 2 nanoparticles prepared by the disclosed process.
  • Figure 2 shows the X-ray diffraction patterns of nanoparticles prepared according to the disclosed process.
  • Figure 3 shows optical spectra of CulnS 2 nanoparticles prepared according to the disclosed process.
  • Figure 4 is a transmission electron micrograph of CulnS 2 nanopartides prepared according to the disclosed process.
  • FIG. 5 shows thermogravametric analysis (TGA) of CulnS 2 nanopartides prepared according to the disclosed process.
  • Figure 6 show absorption spectra of nanopartides prepared according to the disclosed process.
  • Figure 7 is a transmission electron micrograph of nanopartides prepared according to the disclosed process.
  • Figure 8 is a transmission electron micrograph of nanopartides prepared according to the disclosed process.
  • Figure 9 is a transmission electron micrograph of nanopartides prepared according to the disclosed process.
  • Figure 10 is TGA analysis of CulnS 2 nanopartides prepared according to an embodiment of the disclosed process.
  • Figure 1 1 is absorption and photoluminescence spectra of
  • Figure 12 is TGA analysis of Cu(ln,Ga)S 2 nanopartides prepared according to an embodiment of the disclosed process.
  • Figure 13 is absorption and photoluminescence spectra of
  • a preferred embodiment produces nanoparticles having the formula Culn x Gai -x S 2 wherein 0 ⁇ x ⁇ 1 range.
  • the formula CulnS 2 refers to materials comprising Cu, In, and S. It will be understood that the formula does not necessarily indicate that the Cu:ln:S ratio is exactly 1 :1 :2.
  • Cu(ln,Ga)S 2 refers to a material having Cu, In, Ga, and S, but does not necessitate that the Cu:ln:Ga:S ratio is exactly 1 :1 :1 :2.
  • the term "CIGS" is herein used to define any material containing Cu and S and/or In and/or Ga.
  • Nanoparticles can be formed at temperatures as low as 200°C or lower by reacting group 1 1 and group 13 ion sources and an alkane thiol in an organic solvent and promoting the reaction by applying heat.
  • Group 1 1 and group 13 ion sources are generally metal salts, for example, acetate salts or halide salts of the desired metal ion.
  • the thiol compound may be represented by the formula R- SH, where R is a substituted or unsubstituted organic group, (i.e., one or more hydrogen atoms bonded to a carbon atom may be replaced with a non-hydrogen atom).
  • the organic group may be saturated or unsaturated.
  • the organic group is preferably a linear, branched or cyclic organic group, which may be a carboxyl group or a heterocyclic group.
  • the organic group is preferably an alkyl, alkenyl, alkynyl, and/or aryl.
  • the organic group may be an alkyl, alkenyl or alkynyl group containing 2 to 20 carbon atoms, more preferably 4 to 14 carbon atoms and most preferably 10 or less carbon atoms.
  • the thiols serve two purposes in the synthesis. Firstly, they are a source of sulphur for the nanoparticle. Secondly, the thiols act as surface-bound ligands. The thiols bind to the surfaces of the nanoparticles, forming a ligand layer upon the surfaces. The ligand layer can be formed almost exclusively of thiol. In other words, some amount of solvent molecules may adhere to the ligand layer or be intercalated within the layer, but the vast majority of the ligand layer may be formed of thiol ligands. It will also be appreciated that the term "layer" does not necessitate that the ligand layer is a complete monolayer or is limited to one monolayer. Greater or fewer thiol molecules may be present on the nanoparticle surface than a single monolayer.
  • the use of low boiling alkane thiol ligands is advantageous because it facilitate the removal of the ligands from films at relatively low temperatures. Low temperature removal enables low temperature device processing.
  • the surface-bound thiols are ejected from the surface of the nanoparticles when the nanoparticles are heated to 350 °C, or greater.
  • ejected can mean that the thiols decompose, evaporate, or otherwise are removed from the nanoparticle surface.
  • the thiols are ejected when the nanoparticles are heated to 300 °C or greater, 250 °C or greater, or 200 °C or greater.
  • the alkane thiol can contain ten carbons or less, eight carbons or less, or six carbons or less.
  • a particularly suitable alkane thiol is n-octane thiol, which has a boiling point of about 200°C.
  • branched alkane thiols for example, tertiary thiols, can be used.
  • a branched thiol is used as the sulphur source and a short-chain low boiling linear thiol, is used as the capping ligand.
  • CIGS made with tertiary thiols can be synthesized at lower temperatures, allowing the use of short-chained, lower boiling ligands as capping agents.
  • butanethiol is too volatile to be introduced in CIGS synthesized at 200°C, as its boiling point is ⁇ 100°C.
  • butane thiol can be used as a capping ligand in conjunction with a tertiary thiol used as a sulphur source.
  • a tertiary thiol used as a sulphur source is another advantage of the tertiary thiols.
  • one object of the disclosure is to provide nanoparticles having the formula Culn x Gai -x S2 capped with alkyl thiol capping ligands, particularly alkyl thiol capping ligands of ten carbons or less, and preferably eight carbons or less.
  • the capping ligand has less than six carbons.
  • the capping ligand has four carbons.
  • the nanoparticles may be thermally annealed for a certain amount of time at a temperature lower than the reaction temperature (usually ⁇ 40°C lower) to improve the topology and narrow the size distribution.
  • Nanoparticle made using the described process are generally less than 10 nm in diameter and are more typically as small as about 2.5 nm in diameter.
  • the described process provides nanoparticles populations having a high degree of monodispersity.
  • nanoparticles prepared using the described process may exhibit an emission spectrum having a FWHM of less than about 200 nm and more preferably less than about 150 nm or less than about 100 nm.
  • the nanoparticles may be isolated by the addition of a non-solvent and re-dispersed in organic solvents, such as toluene, chloroform and/or hexane to form nanoparticle ink.
  • Additives such as additional thiol, can be incorporated into the reaction solution to tailor the final ink viscosity.
  • a sufficient quantity of the nanoparticles is combined with the ink base such that the resulting ink formulation includes up to around 50% w/v of the nanoparticles, more preferably around 10 to 40% w/v of the nanoparticles, and most preferably around 20 to 30% w/v of the nanoparticles.
  • the nanoparticle concentration may be made as high as possible. It is within the ability of a person of skill to adjust the nanoparticle concentration of the ink to best suit their operational parameters.
  • the nanoparticle ink can be printed onto a supporting layer to form a thin film including nanoparticles incorporating ions selected from groups 1 1 , 13, and 16 of the periodic table.
  • formation of the film includes depositing a formulation containing the nanoparticles by printing, coating or spraying onto a supporting layer under conditions permitting formation of the thin film on the supporting layer.
  • Deposition of the nanoparticle formulation may be achieved using any appropriate method but it preferably includes drop casting, doctor blading and/or spin coating.
  • the spin coating may be effected using a spinning speed of up to around 5000 rpm, more preferably a spinning speed of around 500 to 3500 rpm, and most preferably a spinning speed of around 2000 rpm.
  • the spin coating may be effected over a time period of up to around 300 seconds, more preferably a time period of around 20 to 150 seconds, and most preferably a time period of around 60 seconds.
  • Formation of the film generally includes one or more annealing cycles including a series of steps in which the temperature of the nanoparticle formulation deposited on the supporting layer is repeatedly increased and subsequently maintained at the increased temperature for a predetermined period of time, following which the nanoparticle formulation is cooled to form the film.
  • each of the series of steps is affected to provide an increase in temperature of the nanoparticle formulation of around 10 to 70°C.
  • Initial steps may be effected to provide larger temperature increases than later steps.
  • a first of such steps may effect a temperature increase of around 50 to 70°C, followed by one or more subsequent steps in which the temperature is increased by around 10 to 20°C.
  • Each of the series of steps preferably includes increasing the temperature of the nanoparticle formulation at a rate of up to around 10°C/minute, more preferably at a rate of around 0.5 to 5°C/minute and most preferably at a rate of around 1 to 2°C/minute.
  • initial steps may involve temperature increases at a greater rate than later steps.
  • one or two of the initial steps may include heating to provide temperature increases of around 8 to 10°C/minute, while later steps may involve temperature increases of around 1 to 2°C/minute.
  • each step involves heating and then maintaining the nanopartide-containing formulation at the increased temperature for a predetermined period of time.
  • This solid was dispersed in 25 ml toluene and 25 ml of acetone were added. The mixture was spun in a centrifuge at 4000 rpm for 5 minutes. The dark supernatant was set aside and the gummy solid extracted with a further 20 ml each toluene and acetone. The solid was again isolated by centrifugation (4000 rpm, 5 minutes). The supernatant was combined with the last and the solid was discarded. To the combined supernatants were added 100 ml methanol and 75 ml acetone and the mixture spun at 6500 rpm for 3 minutes. The cloudy, pale orange supernatant was discarded and the remaining dark, oily solid was set aside.
  • the elemental ratio of this compound was found to be Cu1.0ln1.15S1.70 by inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis (13.09 % Cu, 27.32 % In, 1 1 .22 % S by weight).
  • the thiol capping agent contributes to the total sulphur content.
  • the resulting nanoparticles were characterized by an absorption peak at ⁇ 510 nm and weak luminescence at -680 nm which is consistent with the expected quantum confinement effect ( Figures 3 A and 3 B, respectively).
  • the flask was charged with 191 .49g ln(OAc) 3 (0.66 mmol) and 122.39g Cu(OAc) (1 .00 mmol) and placed under vacuum at room temperature. 5 ml of octadecene were injected and the resulting green-colored suspension heated at 100°C under vacuum for 20 minutes. The flask was back-filled with nitrogen and 5 ml of octanethiol (29 mmol) were injected and the temperature was raised to 200°C. As the temperature increased, the solution color turned gradually yellow, orange and finally reddish. The reaction solution was held at 200°C for 10 minutes.
  • the solution was heated at 200°C for 2 hr, then annealed at 160°C for 18 hours. After annealing, the heating was discontinued and the reaction solution was allowed to cool to 60°C. 40 ml of methanol was added and the resulting mixture was stirred at room temperature for 1 hour, followed by a 15-minute period without stirring. The process was repeated one time. A red solid was isolated, washed with 50 ml_ of acetone and collected by centrifugation. The solid was dispersed in 30 ml of dichloromethane, filtered and re- precipitated with 75ml_ of methanol. The solid was re-dispersed in 10 ml_ of dichloromethane, re-precipitated, and isolated.
  • the TGA graph of this material shows a second step at 370°C compared to the sample prepared in octanethiol alone (see Figure 5). This reflects a different behavior of the materials in toluene, with the material prepared with TOP:S having a significantly higher viscosity, despite the total inorganic content being very similar.
  • the cooled reaction mixture was centrifuged at 4000 rpm for 5 minutes. The top oily layer was decanted off and discarded. The solid was dispersed in acetone, then methanol was added and the mixture was centrifuged at 4000 rpm for 5 minutes. The solid was re-dispersed in acetone/methanol and centrifuged. After discarding the supernatant, the process was repeated twice further. The solid was dissolved in dichloromethane, then precipitated with acetone/methanol. After centrifugation at 4000 rpm for 5 minutes, the supernatant was discarded. The process was repeated, then the solid was dried under vacuum overnight, leaving a black solid as the product.
  • Elemental analysis by ICP-OES gave the following content by weight: 16.84 % Cu, 25.25% In, 5.28% Ga, 18.8% S. This corresponds to a stoichiometry of Culno.e3Gao.29S2.21 -
  • the thiol capping agent contributes to the total sulphur content.
  • XRD ( Figure 2 D) showed a characteristic chalcopyrite diffraction pattern, with peak positions and relative intensities intermediate between those of CulnS 2 and CuGaS 2 from the literature.
  • Example 7 Synthesis of Cu(ln,Ga)S 2 nanoparticles [0075] Cu(OAc) (1 .48 g, 12.1 mmol), ln(OAc) 3 (2.82 g, 9.66 mmol), GaCI 3 (0.73 g, 4.1 mmol) and ODE (25 ml_) were loaded into a 250 ml_ round-bottomed flask and degassed at 100°C for 1 hour. 1 -Octanethiol (18 ml_, 104 mmol) was added quickly and the temperature was raised to 125°C, then the solution was annealed for 30 minutes. The temperature was raised to 200°C and the solution was annealed for 2 hours. The temperature was reduced to 160°C and stirred overnight, before cooling to room temperature.
  • Elemental analysis by ICP-OES gave the following content by weight: 16.44% Cu, 24.63% In, 3.86% Ga, 17.67% S. This corresponds to a stoichiometry of Culno.83Gao.21 S2.23-
  • the thiol capping agent contributes to the total sulphur content.
  • XRD ( Figure 2 E) of the material showed a characteristic chalcopyrite diffraction pattern, with peak positions and relative intensities intermediate between those of CulnS2 and CuGaS2 from the literature. The peak appear broader and less defined than those of the CulnGaS 2 prepared with GaC , suggesting that the size of the particles can be tuned by using the appropriate Ga source.
  • TEM revealed nanoparticles ⁇ 3 nm diameter, as shown in Figure 8.
  • Elemental analysis by ICP-OES gave the following content by weight: 13.86 % Cu, 22.05% In, 2.94% Ga, 19.98% S. This corresponds to a stoichiometry of Culno.88Gao.19S2.86-
  • the thiol capping agent contributes to the total sulphur content.
  • the cooled reaction mixture was centrifuged at 4000 rpm for 5 minutes. The top oily layer was decanted off and discarded. The solid was dispersed in acetone, then methanol was added and the mixture was centrifuged at 4000 rpm for 5 minutes. The solid was re-dispersed in acetone/methanol and centrifuged. After discarding the supernatant, the process was repeated. The solid was rinsed twice further with acetone. The solid was dissolved in dichloromethane (DCM), then precipitated with acetone/methanol. After centrifugation at 4000 rpm for 5 minutes, the supernatant was discarded. The process was repeated, then the solid was dried under vacuum for approximately three hours. The oily solid was cleaned with two further portions of DCM/methanol, then dried overnight, leaving a dark brown oily solid as the product.
  • DCM dichloromethane
  • Elemental analysis by ICP-OES gave the following content by weight: 12.74% Cu, 13.42% Ga, 1 1 .54% S. This corresponds to a stoichiometry of CuGao.96Si .go-
  • the thiol capping agent contributes to the total sulphur content.
  • XRD Figure 2 F showed a characteristic chalcopyrite diffraction pattern, which corresponds well to the peak positions and relative intensities of CuGaS 2 from the literature.
  • TEM ( Figure 9) showed aggregates of pseudo-spherical nanoparticles with average diameters of ⁇ 4-5 nm.
  • Methanol 300 ml was added to the combined supernatants and the resulting precipitate was isolated by centrifugation (2700 G, 5 mins). The pale orange supernatant was discarded and the solid was re-precipitated from 10 ml dichloromethane/100 ml methanol before being isolated by centrifugation and dried under vacuum.
  • Methanol 250 ml was added to the combined supernatants and the mixture spun at 2700G for 5 minutes. The pale orange supernatant was discarded and the resulting solid was dispersed in 30 ml of toluene. Propan-2-ol (45 ml) were added and the mixture spun at 2700 G for 5 minutes. The supernatant was set aside and residues left behind were discarded.
  • TGA Figure 12 of the nanoparticles prepared according to the process described in this example shows that all organics associated with the nanoparticles evaporate at temperatures less than 350°C, indicating that oleyamine does not cap the nanoparticles.
  • oleyamine is not incorporated into films prepared using nanoparticles prepared according to this process and does not contribute to residual carbon in the films.

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Abstract

L'invention concerne des nanoparticules contenant des ions du groupe 11 de l'IUPAC, des ions du groupe 13 et des ions de soufre qui sont synthétisées par ajout de sels métalliques et d'un alcanethiol dans un solvant organique et favorisation de la réaction par application de chaleur. Des nanoparticules sont formées à des températures aussi basses que 200°C. Les nanoparticules peuvent être thermiquement recuites pour une certaine durée de temps à une température inférieure à la température de réaction (généralement ~40°C plus faible) pour améliorer la topologie et réduire la distribution de taille. Après que la réaction est achevée, les nanoparticules peuvent être isolées par l'ajout d'un non-solvant et re-dispersées dans des solvants organiques comprenant du toluène, du chloroforme et de l'hexane pour former une encre à nanoparticules. Des additifs peuvent être incorporés dans la solution de réaction pour ajuster la viscosité d'encre finale.
EP14728626.4A 2013-03-04 2014-03-03 Précurseurs de nanoparticules en chalcogénure de cuivre-indium-gallium pour cellules solaires en couches minces Active EP2964566B1 (fr)

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JP7070826B2 (ja) * 2017-02-28 2022-05-18 国立大学法人東海国立大学機構 半導体ナノ粒子およびその製造方法ならびに発光デバイス
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